CN110521290A - The manufacturing method of photosensitive polymer combination, the dry film for having used it, printed wiring board and printed wiring board - Google Patents

The manufacturing method of photosensitive polymer combination, the dry film for having used it, printed wiring board and printed wiring board Download PDF

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Publication number
CN110521290A
CN110521290A CN201780089117.3A CN201780089117A CN110521290A CN 110521290 A CN110521290 A CN 110521290A CN 201780089117 A CN201780089117 A CN 201780089117A CN 110521290 A CN110521290 A CN 110521290A
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China
Prior art keywords
epoxy resin
photosensitive polymer
polymer combination
ingredient
type epoxy
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Granted
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CN201780089117.3A
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CN110521290B (en
Inventor
古室伸仁
代岛雄汰
小岛正幸
入泽真治
大崎真也
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention is provided for projection exposure, the any fine tuning without being formed for directly retouching exposure machine can apply, and it is difficult to happen the missing of undercutting and corrosion-resisting pattern top that corrosion-resisting pattern bottom is cut out, the line width of the middle part (central portion) and most deep (bottom) that are capable of forming on the depth direction in corrosion-resisting pattern section is difficult to the corrosion-resisting pattern of the excellent cross sectional shape of the line width (linearity i.e. on the depth direction of corrosion-resisting pattern profile is good) greater than surface element, and then the photosensitive polymer combination excellent in reliability such as insulating reliability or resistance to cracking, the dry film of the photosensitive polymer combination is used, the manufacturing method of printed wiring board and printed wiring board.Photosensitive polymer combination of the invention contains photopolymerization sensitizer and (D) photopolymerizable compound of (A) epoxy resin, (B) Photoepolymerizationinitiater initiater, (C) containing sour modified vinyl containing benzophenone cpd.

Description

Photosensitive polymer combination, the dry film for having used it, printed wiring board and printing cloth The manufacturing method of line plate
Technical field
The present invention relates to photosensitive polymer combinations, the dry film for having used the photosensitive polymer combination, printed wiring The manufacturing method of plate and printed wiring board.
Background technique
In the manufacturing field of printed wiring board, implement to form permanent mask resist on printed wiring board.Permanently Mask resist is in the use of printed wiring board with the electrical insulating property between the burn into holding conductor layer for preventing conductor layer Effect.In recent years, permanent mask resist by soldering on printed wiring board to semiconductor element carry out flip-chip assembly, Wire bonding assembly etc. process in, also have as prevent solder attachment in the unnecessary portion of the conductor layer of printed wiring board On solder mask effect.
All the time, the permanent mask resist in printed wiring board manufacture is using hot curing resin composition, benefit It is made of silk-screen printing, or uses photosensitive polymer combination, utilizes the production of photo method.For example, so-called having used FC (Flip Chip, flip-chip), TAB (Tape Automated Bonding, tape automated bonding) and COF (Chip On Film, flip chip) assembly method flexible distributing board in, removing IC chip, electronic component or LCD (Liquid Crystal Display, liquid crystal display) part except panel and connecting wiring part, silk-screen printing heat-curing resin paste Expect and carry out heat cure, to form permanent mask resist (referring for example to patent document 1).
In addition, in BGA (Ball Grid Array), the CSP (Chip Size Package) etc. that are equipped on electronic component In conductor package substrate, (1) in order on conductor package substrate by soldering to semiconductor element carry out flip-chip assembly, (2) in order to carry out wire bonding or (3) to semiconductor element and conductor package substrate in order to conductor package substrate to be brazed It is bonded in motherboard substrate, needs to remove the permanent mask resist of its bonding part.Therefore, in the permanent mask resist Formation in, using photosensitive polymer combination is coated it is dry after selectively irradiate ultraviolet light isoreactivity light with Solidify it and only irradiated portion is removed and carried out using development the photo method of image formation.Photo method is due to its operation Property it is good and be suitable for mass production, therefore the image for being widely used in field of electronic materials photosensitive polymer combination is formed (referring for example to patent document 2).The projection that used exposure machine as we all know there are mask non-contact type when being irradiated exposes Ray machine retouches type exposure machine with the straight of mask is not needed.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-198105 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2011-133851 bulletin
Summary of the invention
Subject to be solved by the invention
But due to the difference of Exposing Lamp, the exposure wavelength irradiated is different, and the irradiation with same composition is difficult 's.For example, utilizing if being set as being suitble to the composition for the projection exposure machine that there is main irradiation peak in low wavelength side in long wavelength With main irradiation peak when directly retouching type exposure machine must prolonging exposure time, productivity can decline.Therefore, status is necessary basis Various exposure machines are finely adjusted composition.
In turn, in recent years, with the miniaturization of electronic equipment, high performance, the aperture (opening of permanent mask resist Diameter) distance between centers in size and hole has the tendency that further miniaturizeing, such as is the center in 100 μm and hole using pore size Between distance be 100 μm, pore size is 80 μm and the distance between centers in hole is fine pattern as 80 μm.For example, in upside-down mounting In piece assembly, recently, to photosensitive polymer combination other than requiring resolution ratio, insulating reliability or resistance to cracking are also required Etc. reliabilities raising.
The purpose of the present invention is to provide for projection exposure, directly retouch type exposure machine it is any for without carry out The fine tuning of composition can apply and be difficult to happen missing, the energy of undercutting and corrosion-resisting pattern top that corrosion-resisting pattern bottom is cut out The line width of the middle part (central portion) and most deep (bottom) that are enough formed on the depth direction in corrosion-resisting pattern section is difficult to be greater than table Face line width (linearity i.e. on the depth direction of corrosion-resisting pattern profile (end) is good) excellent cross sectional shape it is against corrosion Pattern and then the photosensitive polymer combination excellent in reliability such as insulating reliability or resistance to cracking, have used the photonasty tree The manufacturing method of the dry film of oil/fat composition, printed wiring board and printed wiring board.
Means for solving the problems
Further investigation has been repeated in the present inventors in order to solve the above problems, as a result, it has been found that, by containing containing acid Further cooperate benzophenone in the composition of the epoxy resin of modified vinyl, Photoepolymerizationinitiater initiater and photopolymerizable compound Compound can be addressed, so as to complete the present invention as photopolymerization sensitizer.That is, the present invention provide it is following photosensitive The manufacturer of property resin combination, the dry film for having used the photosensitive polymer combination, printed wiring board and printed wiring board Method.
[1] a kind of photosensitive polymer combination contains (A) epoxy resin containing sour modified vinyl, (B) photopolymerization is drawn Send out agent, (C) photopolymerization sensitizer and (D) photopolymerizable compound containing benzophenone cpd.
[2] photosensitive polymer combination according to [1], wherein benzophenone cpd contained by above-mentioned (C) ingredient Be at least one be selected from amino, ethylamino, dimethylamino, diethylamino, dibutylamino, hydroxyl, methoxyl group, The benzophenone cpd of group in ethyoxyl, butoxy and phenyl.
[3] photosensitive polymer combination according to [1] or [2], wherein above-mentioned (A) ingredient contains selected from using double At least one kind of epoxy resin (A1) and use containing sour modified vinyl of phenol phenolic resin varnish type epoxy resin (a1) synthesis are different In at least one kind of epoxy resin (A2) containing sour modified vinyl that the epoxy resin (a2) of the epoxy resin (a1) synthesizes extremely It is a kind few.
[4] photosensitive polymer combination according to [3], wherein above-mentioned epoxy resin (a2) is selected from novolaks It is at least one kind of in type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin and tris-phenol type epoxy resin.
[5] photosensitive polymer combination according to [3] or [4], wherein the above-mentioned asphalt mixtures modified by epoxy resin containing sour modified vinyl Rouge (A1) be make containing saturation or unsaturated group multi-anhydride (c) and make above-mentioned epoxy resin (a1) and containing the unitary of vinyl Resin (A1 ') made of carboxylic acid (b) reaction reacts and the resin that is formed, the above-mentioned epoxy resin containing sour modified vinyl (A2) be make containing saturation or unsaturated group multi-anhydride (c) with make each above-mentioned epoxy resin (a2) and containing vinyl one Resin (A2 ') made of the reaction of first carboxylic acid (b) reacts and the resin that is formed.
[6] photosensitive polymer combination according to any one of [3]~[5], wherein above-mentioned bis-phenol phenolic varnish type Epoxy resin (a1) is selected from the bis-phenol phenolic resin varnish type epoxy resin with structural unit shown in the following general formula (I) and to have It is at least one kind of in the bis-phenol phenolic resin varnish type epoxy resin of structural unit shown in the following general formula (II),
[chemical formula number 1]
(in logical formula (I), R11Indicate hydrogen atom or methyl, Y1And Y2Each independently represent hydrogen atom or glycidyl. Multiple R11It may be the same or different, Y1And Y2At least one of indicate glycidyl.〕
[chemical formula number 2]
(in logical formula (II), R12Indicate hydrogen atom or methyl, Y3And Y4Each independently represent hydrogen atom or glycidol Base.Multiple R12It may be the same or different, Y3And Y4At least one of indicate glycidyl.〕
Above-mentioned epoxy resin (a2) is selected from the nobolak type epoxy with structural unit shown in the following general formula (III) Resin, the bisphenol-type epoxy resin with structural unit shown in the following general formula (IV) and have the following general formula (V) shown in tie It is at least one kind of in the tris-phenol type epoxy resin of structure unit.
[chemical formula number 3]
(in logical formula (III), R13Indicate hydrogen atom or methyl, Y5Indicate hydrogen atom or glycidyl, and hydrogen atom and contracting The glyceryl molar ratio of water (hydrogen atom/glycidyl) is 0/100~30/70.〕
[chemical formula number 4]
(in logical formula (IV), R14Indicate hydrogen atom or methyl, Y6Indicate hydrogen atom or glycidyl, and hydrogen atom and contracting The glyceryl molar ratio of water (hydrogen atom/glycidyl) is 0/100~30/70, multiple R14Can it is identical not yet Together.〕
[chemical formula number 5]
(in logical formula (V), Y7Indicate hydrogen atom or glycidyl, multiple Y7It may be the same or different, at least one Y7For Glycidyl.〕
[7] photosensitive polymer combination according to any one of [3]~[6], wherein above-mentioned (A) ingredient contain to Few a kind of above-mentioned epoxy resin (A1) and at least one kind of above-mentioned epoxy resin containing sour modified vinyl containing sour modified vinyl (A2)。
[8] photosensitive polymer combination according to [7], wherein above-mentioned bis-phenol phenolic resin varnish type epoxy resin (a1) With structural unit shown in above-mentioned logical formula (I), and above-mentioned epoxy resin (a2) is to contain structure shown in above-mentioned logical formula (IV) The bisphenol A type epoxy resin or bisphenol f type epoxy resin of unit.
[9] photosensitive polymer combination according to any one of [3]~[6], wherein above-mentioned (A) ingredient contain to Few a kind of above-mentioned epoxy resin (A2) containing sour modified vinyl.
[10] photosensitive polymer combination according to [9], wherein above-mentioned epoxy resin (a2) is with above-mentioned general formula (III) phenolic resin varnish type epoxy resin of structural unit shown in.
[11] photosensitive polymer combination according to any one of [1]~[10], wherein above-mentioned (B) photopolymerization is drawn Sending out agent is selected from alkyl phenones system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater, luxuriant titanium system Photoepolymerizationinitiater initiater And it is at least one kind of in oxime ester system Photoepolymerizationinitiater initiater.
[12] photosensitive polymer combination according to any one of [1]~[11], wherein above-mentioned (B) photopolymerization is drawn Sending out agent is selected from alkyl phenones system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and oxime ester system Photoepolymerizationinitiater initiater In it is at least one kind of.
[13] photosensitive polymer combination according to any one of [1]~[12], wherein above-mentioned (B) photopolymerization is drawn Hair agent is acylphosphine oxide system Photoepolymerizationinitiater initiater.
[14] photosensitive polymer combination according to any one of [1]~[13], further contains (E) pigment.
[15] photosensitive polymer combination according to any one of [1]~[14], further contains that (F) is inorganic to be filled out Fill object.
[16] a kind of dry film, the photoresist with carrier film and described in any one of having used [1]~[15] The photosensitive layer of composition.
[17] a kind of printed wiring board has the photosensitive polymer combination shape as described in any one of [1]~[15] At permanent mask resist.
[18] printed wiring board according to [17], wherein above-mentioned permanent mask resist with a thickness of 10 μm or more.
[19] a kind of manufacturing method of printed wiring board, successively contains following processes:
It is used on substrate described in photosensitive polymer combination described in any one of [1]~[15] or claim 16 Dry film is arranged the process of photosensitive layer；
The process for forming corrosion-resisting pattern using the photosensitive layer；And
The corrosion-resisting pattern is carried out to the process for being solidified to form permanent mask resist.
Invention effect
In accordance with the invention it is possible to provide for projection exposure, directly retouch type exposure machine it is any for without carry out The fine tuning of composition can apply and be difficult to happen missing, the energy of undercutting and corrosion-resisting pattern top that corrosion-resisting pattern bottom is cut out The line width of the middle part (central portion) and most deep (bottom) that are enough formed on the depth direction in corrosion-resisting pattern section is difficult to be greater than table In the line width (linearity i.e. on the depth direction of corrosion-resisting pattern profile is good) of face, the depth direction of corrosion-resisting pattern profile The corrosion-resisting pattern of the good excellent cross sectional shape of linearity and then the photonasty tree excellent with the adaptation and mobility of copper base Oil/fat composition has used the dry film of the photosensitive polymer combination, the manufacturing method of printed wiring board and printed wiring board.
Detailed description of the invention
Fig. 1 is the signal of the excellent resist cross sectional shape of the linearity on the depth direction for indicate corrosion-resisting pattern profile Figure.
Fig. 2 is the schematic diagram of the resist cross sectional shape of the linearity difference on the depth direction for indicate corrosion-resisting pattern profile.
Specific embodiment
[photosensitive polymer combination]
The photosensitive polymer combination of embodiment of the present invention (being simply referred to as present embodiment sometimes later) contains (A) containing acid Photopolymerization sensitizer containing benzophenone cpd of the epoxy resin of modified vinyl, (B) Photoepolymerizationinitiater initiater, (C) and (D) photopolymerizable compound.In this specification, these ingredients be simply referred to as sometimes (A) ingredient, (B) ingredient, (C) ingredient, (D) at Point etc..
The photosensitive polymer combination of present embodiment is by can be improved the light of corrosion-resisting pattern bottom with above-mentioned composition Curability is not required to increase ultraviolet therefore, it is difficult to which the missing of undercutting and corrosion-resisting pattern top that corrosion-resisting pattern bottom is cut out occurs The light exposure of line irradiation, it is thus possible to form the excellent thick resist pattern of linearity on the depth direction of corrosion-resisting pattern profile Case.In turn, the photosensitive polymer combination of present embodiment with the adaptation of copper base by becoming with above-mentioned specific composition Obtaining excellent and mobility becomes excellent.In addition, to required by printed wiring board photosensitive polymer combination used in manufacture The basic performances such as electrical insulating property, soldering heat resistance, thermal shock resistance, solvent resistance, acid resistance, alkali resistance also become excellent.
It is described below for each ingredient.
Epoxy resin > of the < (A) containing sour modified vinyl
The photosensitive polymer combination of present embodiment contains (A) ingredient.(A) ingredient is with the organic acid pair containing vinyl The substance that epoxy resin is modified, such as can enumerate and make multi-anhydride containing saturated group or unsaturated group and make epoxy Resin and monocarboxylic acid containing vinyl react epoxy resin made of resin obtained reacts.
As (A) ingredient, such as can enumerate using bis-phenol phenolic resin varnish type epoxy resin (a1) (later sometimes referred to as (a1) Ingredient) synthesis epoxy resin (A1) (sometimes referred to as (A1) ingredient) containing sour modified vinyl later, use the epoxy resin (a1) epoxy resin containing sour modified vinyl of epoxy resin (a2) (sometimes referred to as (a2) ingredient later) synthesis other than (A2) (sometimes referred to as (A2) ingredient later) etc., these substances may be used singly or in combin a variety of.In addition, from being difficult to The missing of undercutting and resist top occurs, improves the linearity, close with copper base on the depth direction of corrosion-resisting pattern profile From the perspective of conjunction property and mobility, (A) ingredient can contain at least one kind of (A1) ingredient and use for using (a1) ingredient to synthesize (a2) at least one kind of (A2) ingredient of ingredient synthesis.
(epoxy resin (a1))
As (A) ingredient, from being difficult to happen the missing of undercutting and resist top, improve the depth side of corrosion-resisting pattern profile Upward linearity, with from the perspective of the adaptation and mobility of copper base, and then from the warpage (warpage for reducing film substrate Reduction property), improve thermal shock resistance, from the perspective of resolution ratio, preferably comprise (A1) ingredient that uses (a1) ingredient synthesizes.From From the perspective of being identical with this, as (a1) ingredient, preferably there is the bis-phenol of structural unit shown in the following general formula (I) or (II) Phenolic resin varnish type epoxy resin can more preferably enumerate the bis-phenol novolaks type ring with structural unit shown in logical formula (II) Oxygen resin.
(epoxy resin with structural unit shown in logical formula (I))
(a1) preferred embodiment of ingredient first is that the epoxy resin with structural unit shown in the following general formula (I).
[chemical formula number 6]
In logical formula (I), R11Indicate hydrogen atom or methyl, Y1And Y2Each independently represent hydrogen atom or glycidyl. Multiple R11It may be the same or different, Y1And Y2At least one of indicate glycidyl.
R11Straight line from the missing for being difficult to happen undercutting and resist top, the depth direction for improving corrosion-resisting pattern profile From the perspective of property, resolution ratio, preferably hydrogen atom.In addition, from the viewpoint of identical, so from improve thermal shock resistance, From the perspective of warpage reduction property, preferably Y1And Y2For glycidyl.
The structural unit number of the structural unit in 1 molecule of (a1) ingredient with structural unit shown in logical formula (I) For 1 or more number, suitably selected preferably from 10~100,15~80 or 15~70.Structural unit number is above range When interior, the resist shape that the linearity that can be formed on the depth direction of corrosion-resisting pattern profile increases, with copper base Adaptation, heat resistance and electrical insulating property improve.Here, the structural unit number of structural unit is formed in (a1) ingredient by a kind of molecule When show integer value, rational of the display as average value when for the aggregate of different kinds of molecules.Hereinafter, for structural unit Structural unit number is same.
(epoxy resin with structural unit shown in logical formula (II))
In addition, (a1) ingredient is another it is preferable that the asphalt mixtures modified by epoxy resin with structural unit shown in the following general formula (II) Rouge.
[chemical formula number 7]
In logical formula (II), R12Indicate hydrogen atom or methyl, Y3And Y4Each independently represent hydrogen atom or glycidyl. Multiple R12It may be the same or different, Y3And Y4At least one of indicate glycidyl.
R12Straight line from the missing for being difficult to happen undercutting and resist top, the depth direction for improving corrosion-resisting pattern profile From the perspective of property, resolution ratio, preferably hydrogen atom.
In addition, from the viewpoint of identical, and then from the viewpoint of improving thermal shock resistance, warpage reduction property, Y3And Y4 Preferably glycidyl.
The structural unit number of the structural unit in 1 molecule of (a1) ingredient with structural unit shown in logical formula (II) For 1 or more number, suitably selected preferably from 10~100,15~80 or 15~70.Structural unit number is above range When interior, the resist shape that the linearity that can be formed on the depth direction of corrosion-resisting pattern profile increases, with copper base Adaptation, heat resistance and electrical insulating property improve.
In logical formula (II), R12For hydrogen atom, Y3And Y4It for example can be used as EXA-7376 series (DIC for glycidyl person Co. Ltd. system, trade name) it buys, in addition, R12For methyl, Y3And Y4It for example can be used as EPON SU8 for glycidyl person Serial (Japan Epoxy Resin Co. Ltd. system, trade name) is bought.
(epoxy resin (a2))
(a2) it as long as the epoxy resin that ingredient is different from (a1) ingredient is then not particularly limited, undercuts and resists from being difficult to happen Lose the missing on agent top, improve linearity on the depth direction of corrosion-resisting pattern profile, with the adaptation of copper base and mobility, And from the perspective of improving resolution ratio, it is preferably selected from phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, Bisphenol F type ring It is at least one kind of in oxygen resin and tris-phenol type epoxy resin.
As phenolic resin varnish type epoxy resin, can preferably enumerate with structural unit person shown in the following general formula (III), As bisphenol A type epoxy resin or bisphenol f type epoxy resin, can preferably enumerate with structure list shown in the following general formula (IV) First person can preferably enumerate as tris-phenol type epoxy resin with structural unit person shown in the following general formula (V).
(a2) ingredient be more preferably selected from the phenolic resin varnish type epoxy resin with structural unit shown in logical formula (III) with And it is at least one kind of in the bisphenol A type epoxy resin and bisphenol f type epoxy resin with structural unit shown in logical formula (IV), it is right In the resin with structural unit shown in logical formula (IV), preferably bisphenol f type epoxy resin.
In addition, preferably being formed without using utilization (a1) ingredient from the viewpoint of taking into account photobehavior and insulating reliability (A1) ingredient, (a2) ingredient be the phenolic resin varnish type epoxy resin with structural unit shown in above-mentioned logical formula (III).Separately Outside, from the viewpoint of improving thermal shock resistance, warpage reduction property and resolution ratio, particularly preferred (A) ingredient contains (A1) ingredient And (A2) ingredient, particularly (a1) ingredient are the bis-phenol nobolak type epoxy containing structural unit shown in above-mentioned logical formula (II) Resin and (a2) ingredient are bisphenol A type epoxy resin or bisphenol F type epoxy containing structural unit shown in above-mentioned logical formula (IV) The combination of resin.Here, refer to " without using (A1) ingredient " and contain substantially no, indicate the solid component total amount in (A) ingredient In, the content of (A1) ingredient is less than 5 mass %, any case less than 1 mass % or less than 0.5 mass %.
(epoxy resin with structural unit shown in logical formula (III))
As (a2) ingredient, it is clear that the phenolic aldehyde with structural unit shown in the following general formula (III) can be enumerated as preference Paint shaped epoxy resin as the phenolic resin varnish type epoxy resin with this structural unit, such as can enumerate the following general formula Phenolic resin varnish type epoxy resin shown in (III ').
[chemical formula number 8]
Lead in formula (III) and (III '), R13Indicate hydrogen atom or methyl, Y5Indicate hydrogen atom or glycidyl, and hydrogen The molar ratio (hydrogen atom/glycidyl) of atom and glycidyl is 0/100~30/70.In addition, in general formula (III '), n1For 1 or more number, multiple R13And Y5It may be the same or different, Y5In at least one indicate glycidyl.
R13Straight line from the missing for being difficult to happen undercutting and resist top, the depth direction for improving corrosion-resisting pattern profile From the perspective of property, resolution ratio, preferably hydrogen atom.
In addition, in (a2) ingredient with structural unit shown in logical formula (III) and shown in general formula (III ') (a2) It is the Y of hydrogen atom in ingredient5With the Y for glycidyl5Molar ratio (hydrogen atom/glycidyl) from be difficult to happen undercutting And resist top missing, improve linearity on the depth direction of corrosion-resisting pattern profile, be 0/ from the perspective of resolution ratio It 100~30/70, is preferably 0/100~10/90.It will also realize that by the molar ratio, Y5In at least one be glycidyl.
The structural unit of the structural unit in 1 molecule of (a2) ingredient with structural unit shown in logical formula (III) N in several and general formula (III ')1Shown in number be 1 or more numbers, preferably from 10~200,30~150 or 30~100 fit When selection.n1When in above range, the linearity that can be formed on the depth direction of corrosion-resisting pattern profile increases Resist shape, improved with the adaptation, heat resistance and electrical insulating property of copper base.
As phenolic resin varnish type epoxy resin shown in logical formula (III), phenol novolak type epoxy resin, first can be enumerated Phenol phenolic resin varnish type epoxy resin.These phenolic resin varnish type epoxy resins for example can be by making phenol phenol using well known method Novolac resin, cresol novolac resin and epichlorohydrin reaction obtain.
As phenol novolak type epoxy resin or cresol novolak type epoxy resin shown in general formula (III '), example Such as it is commercially available YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (the above are Chemical plants of formula meetings of Dow by (the above are Nippon Steel Chemical Co., Ltd's systems, trade name), CEN-431, CEN-439 Society's system, trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN- 1027, BREN (the above are Nippon Kayaku K. K's systems, trade name), EPN-1138, EPN-1235, EPN-1299 (the above are BASF AG's system, trade name), (the above are DIC plants by N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 Formula commercial firm system, trade name) etc..
(epoxy resin with structural unit shown in logical formula (IV))
As (a2) ingredient, the bisphenol-A with structural unit shown in the following general formula (IV) can be further preferably enumerated Type epoxy resin or bisphenol f type epoxy resin as the epoxy resin with this structural unit, such as can enumerate general formula Bisphenol A type epoxy resin shown in (IV ') or bisphenol f type epoxy resin.
[chemical formula number 9]
Lead in formula (IV) and (IV '), R14Indicate hydrogen atom or methyl, Y6Indicate hydrogen atom or glycidyl, and hydrogen is former The molar ratio (hydrogen atom/glycidyl) of son and glycidyl is 0/100~30/70.In addition, multiple R14It can phase Together can also be different, in general formula (IV '), n2Indicate 1 or more number, n2When being 2 or more, multiple Y6It may be the same or different, at least 1 A Y6For glycidyl.
R14Straight line from the missing for being difficult to happen undercutting and resist top, the depth direction for improving corrosion-resisting pattern profile From the perspective of property, resolution ratio, preferably hydrogen atom.
In addition, from the viewpoint of identical, and then from the viewpoint of improving thermal shock resistance, warpage reduction property, Y6It is excellent It is selected as glycidyl.
In addition, having in (a2) ingredient of structural unit shown in logical formula (IV) and (a2) ingredient shown in general formula (IV ') In, it is the Y of hydrogen atom6With the Y for glycidyl6Molar ratio (hydrogen atom/glycidyl) from improve thermal shock resistance and It is 0/100~30/70, preferably 0/100~10/90 from the perspective of low warpage properties.In logical formula (IV), preferably at least 1 Y6 For glycidyl.
The structural unit number of the structural unit in 1 molecule of (a2) ingredient with structural unit shown in logical formula (IV) And the n in general formula (IV ')2Shown in number indicate 1 or more number, it is appropriate preferably from 10~100,10~80 or 15~60 Selection.n2When in above range, what the linearity that can be formed on the depth direction of corrosion-resisting pattern profile increased Resist shape is improved with the adaptation, heat resistance and electrical insulating property of copper base.
Shown in general formula (IV '), Y6For glycidyl bisphenol A type epoxy resin or bisphenol f type epoxy resin for example It can be by making the hydroxyl and epoxy chloropropionate of bisphenol A type epoxy resin shown in the following general formula (IV ") or bisphenol f type epoxy resin Alkane reacts to obtain.
[chemical formula number 10]
In general formula (IV "), R14And n2With meaning same as described above.
In order to promote reacting for hydroxyl and epoxychloropropane, at being preferably 50~120 DEG C in reaction temperature, in alkali metal hydrogen It is reacted in the presence of oxide, in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide isopolarity organic solvent. When reaction temperature is in above range, reaction will not be become too slow, and can inhibit side reaction.
As bisphenol A type epoxy resin or bisphenol f type epoxy resin shown in general formula (IV '), such as it is commercially available (the above are Japan Epoxy Resin by Epikote 807,815,825,827,828,834,1001,1004,1007 and 1009 Co. Ltd. system, trade name), (the above are Dow Chemical Co. Ltd. systems, commodity by DER-330, DER-301, DER-361 Name), (the above are Nippon Steel by YD-8125, YDF-170, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 Chemical Co., Ltd. system, trade name) etc..
(epoxy resin with structural unit shown in logical formula (V))
As (a2) ingredient, the trisphenol with structural unit shown in the following general formula (V) can be further preferably enumerated Methane type epoxy resin as the tris-phenol type epoxy resin with this structural unit, such as is preferably enumerated logical Tris-phenol type epoxy resin shown in formula (V ').
[chemical formula number 11]
Lead in formula (V) and (V '), Y7Indicate hydrogen atom or glycidyl, multiple Y7It may be the same or different, at least one Y7For glycidyl.In addition, in general formula (V '), n3Indicate 1 or more number.
It is hydrogen in (a2) ingredient with structural unit shown in logical formula (V) and in (a2) ingredient shown in general formula (V ') The Y of atom7With the Y for glycidyl7Molar ratio (hydrogen atom/glycidyl) from being difficult to happen on undercutting and resist The missing in portion improves linearity on the depth direction of corrosion-resisting pattern profile, from the perspective of resolution ratio, preferably 0/100~ 30/70, from this within the scope of suitably select.It will also realize that by the molar ratio, Y7In at least one be glycidyl.
The structural unit number of the structural unit in 1 molecule of (a2) ingredient with structural unit shown in logical formula (V) And the n in general formula (V ')3Shown in number indicate 1 or more number, preferably suitably selected from 10~100,15~80 or 15~70 It selects.n3When in above range, the linearity that can be formed on the depth direction of corrosion-resisting pattern profile increases anti- Dosage form shape is lost, is improved with the adaptation, heat resistance and electrical insulating property of copper base.
As tris-phenol type epoxy resin shown in general formula (V '), such as it is commercially available FAE-2500, EPPN- 501H, EPPN-502H (the above are Nippon Kayaku K. K's systems, trade name) etc..
(A1) ingredient and (A2) ingredient are from linearity, the viewpoint of resolution ratio on the depth direction for improving corrosion-resisting pattern profile Set out, preferably make containing saturation or unsaturated group multi-anhydride (hereinafter sometimes referred to as (c) ingredient) and make (a1) ingredient and (a2) ingredient (hereinafter sometimes referred to as " (a) ingredient ") and the monocarboxylic acid (b) (hereinafter sometimes referred to as (b) ingredient) containing vinyl are anti- Resin made of answering (A1 ') and the resin of (A2 ') (being referred to as " (A ') ingredient " together sometimes below) reaction and formation.
(monocarboxylic acid (b) containing vinyl)
As (b) ingredient, such as preferably enumerate acrylic acid, the dimer of acrylic acid, methacrylic acid, β-furfuryl group third The acrylic acid derivatives such as olefin(e) acid, β-styrene acrylic, cinnamic acid, crotonic acid, alpha-cyano cinnamic acid, as the third of hydroxyl The half ester compound of the reaction product of olefin(e) acid ester and dibasic acid anhydride, as the glycidyl ether of list containing vinyl or list containing vinyl The half ester compound etc. of the reaction product of glycidyl esters and dibasic acid anhydride.
Half ester compound for example passes through acrylate, the glycidyl ether of list containing vinyl with equimolar than making hydroxyl Or the glycidyl esters of list containing vinyl are reacted with dibasic acid anhydride to obtain.These (b) ingredient, which can be used alone or combine, to be made With a variety of.
As hydroxyl used in the synthesis in the above-mentioned half ester compound for (b) ingredient an example acrylate, contain Vinyl list glycidyl ether, the glycidyl esters of list containing vinyl, such as Hydroxyethyl Acrylate, metering system can be enumerated Sour hydroxy methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, methacrylic acid hydroxyl fourth Ester, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trihydroxy methyl Propane dimethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, five propylene of dipentaerythritol Acid esters, pentaerythrite pentamethacrylate, glycidyl acrylate, methyl propenoic acid glycidyl base ester etc..
Dibasic acid anhydride used in synthesis as above-mentioned half ester compound can be enumerated containing saturated group person, containing not Saturated group person.As the specific example of dibasic acid anhydride, succinic anhydride, maleic anhydride, tetrahydro phthalate anhydride, benzene two can be enumerated Formic anhydride, methyl tetrahydro phthalate anhydride, ethyl tetrahydro phthalate anhydride, hexahydrophthalic acid anhydride, methyl hexahydro phthalic acid Acid anhydride, ethyl hexahydrophthalic acid anhydride, itaconic anhydride etc..
In the reacting of above-mentioned (a) ingredient and (b) ingredient, relative to 1 equivalent of epoxy group of (a) ingredient, preferably with (b) ingredient The ratio for reaching 0.5~1.5 equivalent makes its reaction, more preferably reacts it, further to reach the ratio of 0.6~1.05 equivalent It is preferred that making its reaction to reach the ratio of 0.8~1.0 equivalent.By making its reaction with this ratio, it is light that optical polymerism, which improves, Sensitivity increases, therefore the linearity on the depth direction of corrosion-resisting pattern profile improves.
(a) ingredient and make its reaction after (b) ingredient is soluble in organic solvent.
As organic solvent, such as preferably enumerate the ketones such as methyl ethyl ketone, cyclohexanone；Toluene, dimethylbenzene, durol Etc. aromatic hydrocarbon；Methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropyl The glycol ethers such as glycol list ethylether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether；Ethyl acetate, butyl acetate, fourth The esters such as base cellosolve acetate, carbitol acetate；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, hydrogenation stone Petroleum series solvent such as cerebrol, solvent naphtha etc..
In turn, in order to promote the reacting, it is preferable to use catalyst of (a) ingredient and (b) ingredient.As catalyst, such as can Enumerate triethylamine, benzyimethylamine, methyl triethyl ammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyl Base trimethyl ammonium iodide, triphenylphosphine etc..
Total amount 100 mass parts of the usage amount of catalyst relative to (a) ingredient and (b) ingredient, preferably from 0.01~10 Mass parts, the more preferably suitably selection from 0.05~2 mass parts, further preferably from 0.1~1 mass parts.It is upper When stating usage amount, reacting for (a) ingredient and (b) ingredient can promote.
In addition, it is preferable to use polymerization inhibitor for the purpose of preventing the polymerization in reaction.As polymerization inhibitor, such as hydrogen can be enumerated Quinone, methylnaphthohydroquinone, Hydroquinone monomethylether, catechol, pyrogallol etc..
The usage amount of polymerization inhibitor from the viewpoint of the storage stability for improving composition, relative to (a) ingredient and (b) at Point 100 mass parts of total amount, preferably from 0.01~1 mass parts, more preferably from 0.02~0.8 mass parts, further preferably Ground is suitably selected from 0.04~0.5 mass parts.
(a) reaction temperature of ingredient and (b) ingredient is from the viewpoint of productivity, preferably from 60~150 DEG C, more preferably Ground is suitably selected from 80~120 DEG C, further preferably from 90~110 DEG C of range.
In this way, (A ') ingredient made of reacting (a) ingredient with (b) ingredient speculates the epoxy group become through (a) ingredient The substance with hydroxyl formed with the opening of the carboxyl of (b) ingredient.
Speculate by further making to react containing saturation or (c) ingredient of unsaturated group and (A ') ingredient of above-mentioned acquisition, Half ester occurs for the hydroxyl (also including the hydroxyl being originally present in (a) ingredient) and the anhydride group of (c) ingredient for becoming (A ') ingredient Epoxy resin containing sour modified vinyl made of change.
(multi-anhydride (c))
As (c) ingredient, can be used containing saturated group person, person containing unsaturated group.Concrete example as (c) ingredient Son can enumerate succinic anhydride, maleic anhydride, tetrahydro phthalate anhydride, phthalate anhydride, methyl tetrahydro phthalate anhydride, ethyl Tetrahydro phthalate anhydride, hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, ethyl hexahydrophthalic acid anhydride, itaconic anhydride Deng.Wherein, from the viewpoint of obtaining and being capable of forming the photosensitive polymer combination of the pattern of excellent in resolution, preferred tetrahydro benzene Dicarboxylic acid anhydride.
In the reacting of (A ') ingredient and (c) ingredient, for example, by relative in (A ') ingredient 1 equivalent of hydroxyl, make (c) 0.1~1.0 equivalent reaction of ingredient, the acid value of the adjustable epoxy resin containing sour modified vinyl.
(A) acid value of ingredient is preferably 30~150mgKOH/g, more preferably 40~120mgKOH/g, is more preferably 50~100mgKOH/g.When acid value is 30mgKOH/g or more, dissolubility of the photosensitive polymer combination in dilute alkaline soln is excellent Different, when being 150mgKOH/g or less, the electrical characteristics of cured film are improved.
The reaction temperature of (A ') ingredient and (c) ingredient from the viewpoint of productivity, preferably from 50~150 DEG C, it is more excellent Selection of land is suitably selected from 60~120 DEG C, further preferably from 70~100 DEG C of range.
In addition, as needed, as (a) ingredient, for example, can also partially and use bisphenol-A epoxy resin.In turn, It, can also part and with (methyl) Hydroxyethyl Acrylate modifier etc. of styrene-maleic anhydride copolymer as (A) ingredient Styrene-maleic acid system resin.
(molecular weight of (A) ingredient)
(A) weight average molecular weight of ingredient is preferably 3,000~150,000, is more preferably 3,000~30,000, is further Preferably 4,000~25,000,5,000~18,000 are particularly preferably.When in above range, it is capable of forming corrosion-resisting pattern wheel The resist shape that linearity on wide depth direction increases, adaptation, heat resistance and electrical insulating property with copper base It improves.Here, weight average molecular weight is using the gel permeation chromatography measurement using tetrahydrofuran as solvent, polyethylene conversion Weight average molecular weight.More specifically, such as it can make to be measured under following GPC measurement devices and determination condition, use Value obtained from the standard curve of standard polystyren is converted is as weight average molecular weight.In addition, in the production of standard curve, As standard polystyren, 5 sample boxes (" PStQuick MP-H " and " PStQuick B ", Tosoh Co., Ltd. are used System).
(GPC measurement device)
GPC device: high speed GPC device " HCL-8320GPC ", detector are Differential refractometer or UV, Tosoh Co., Ltd. System
Chromatographic column: column TSKgel SuperMultipore HZ-H (column length: 15cm, column internal diameter: 4.6mm), Tosoh plants of formulas Commercial firm's system
(determination condition)
Solvent: tetrahydrofuran (THF)
Measuring temperature: 40 DEG C
Flow: 0.35ml/ minutes
Sample solution concentration: 10mg/THF5ml
Injection rate: 20 μ l
(content of (A) ingredient)
The content of (A) ingredient in photosensitive polymer combination is tried from the heat resistance, electrical characteristics and chemically-resistant for improving film From the perspective of agent, counted on the basis of the solid component total amount of photosensitive polymer combination, preferably from 20~80 mass %, More preferably suitably selected from 30~70 mass %, further preferably in the range of 30~50 mass %.This explanation In book, " solid component " refer to the volatile substances such as water, diluent contained by the photosensitive polymer combination other than it is non-volatile Ingredient, referring to will not evaporate in the dry resin combination, volatilize and remaining ingredient, be additionally comprised in 25 DEG C or so It is at room temperature liquid, malt sugar shape and wax-like ingredient.
(total content of (A1) ingredient and (A2) ingredient in (A) ingredient)
(A1) ingredient and (A2) as (A) ingredient, when (A1) ingredient and (A2) ingredient is applied in combination, in (A) ingredient Resist shape that total content of ingredient increases from the linearity on the depth direction for being capable of forming corrosion-resisting pattern profile, From the perspective of improving chemically-resistant plating and soldering heat resistance, preferably from 80~100 mass %, more preferably from 90~ 100 mass %, it is suitably selected further preferably in the range of 95~100 mass %.In addition, be used alone (A1) at Point, (A2) ingredient when, and from above range suitably select.
(mass ratio of (A1) ingredient and (A2) ingredient)
As (A) ingredient, when (A1) ingredient and (A2) ingredient is applied in combination, mass ratio (A1/A2) is from being capable of forming Resist shape, raising chemically-resistant plating and the soldering that linearity on the depth direction of corrosion-resisting pattern profile increases are resistance to From the perspective of hot, preferably from 20/80~90/10, more preferably from 20/80~80/20, further preferably from 30/ It is suitably selected in the range of 70~70/30.
< (B) Photoepolymerizationinitiater initiater >
As (B) ingredient used in present embodiment, as long as aftermentioned (D) ingredient can be made to polymerize, then without special limit It is fixed, it can suitably be selected from usually used Photoepolymerizationinitiater initiater.For example, can enumerate alkyl phenones system Photoepolymerizationinitiater initiater, The known light such as acylphosphine oxide system Photoepolymerizationinitiater initiater, luxuriant titanium system Photoepolymerizationinitiater initiater, oxime ester system Photoepolymerizationinitiater initiater Polymerization initiator, these Photoepolymerizationinitiater initiaters can be used alone, and can also be applied in combination a variety of.Wherein, from being capable of forming Resist shape, raising chemically-resistant plating and the soldering that linearity on the depth direction of corrosion-resisting pattern profile increases are resistance to , it is preferable to use alkyl phenones system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater, oxime ester system from the perspective of hot Photoepolymerizationinitiater initiater particularly preferably uses alkyl phenones system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater.
As alkyl phenones system Photoepolymerizationinitiater initiater, such as 2- methyl-1-(4- methylthiophenyi)-2- morpholine can be enumerated Generation -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,2,2- dimethoxy -1,2- diphenyl The benzyl dimethyl ketals system such as ethane -1- ketone Photoepolymerizationinitiater initiater；1- hydroxy-cyclohexyl-phenyl -one, 2- hydroxy-2-methyl- 1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyl - The Alpha-hydroxies alkyl phenones systems such as 1- { 4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] phenyl } -2- methyl-propan -1- ketone Photoepolymerizationinitiater initiater；2- methyl-1-[4- (methyl thio) phenyl]-2- morpholinopropanone-1,2- benzyl-2- dimethylamino- 1- (4- morphlinophenyl)-butane -1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholine Base) phenyl] -1- butanone, N, Norleucyls benzene series Photoepolymerizationinitiater initiater such as N- dimethylamino acetyl benzene etc. can be used alone It a kind or is applied in combination a variety of.
As acylphosphine oxide system Photoepolymerizationinitiater initiater, as long as having acylphosphine oxide base (=P (=O)-C (=O)- Base) compound be then not particularly limited, such as (2,6- Dimethoxybenzoyl) -2,4,4- amyl phosphine oxide, 2 can be enumerated, 4,6- trimethyl benzoyl diphenyl base phosphine oxide, ethyl -2,4,6- trimethylbenzoyl phenyl phosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphine oxide, (2,5- dihydroxy phenyl) diphenyl phosphine oxide, the oxidation of (p-hydroxybenzene) diphenyl Phosphine, bis- (p-hydroxybenzene) phenyl phosphine oxides and three (p-hydroxybenzene) phosphine oxides, bis- (2,6- Dimethoxybenzoyls)- 2,4,4- trimethyl-pentyl phosphine oxides etc., can be used alone or be applied in combination and is a variety of.
As luxuriant titanium system Photoepolymerizationinitiater initiater, such as bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- can be enumerated Fluoro- 3- (1H- pyrroles -1- base)-phenyl) titanium etc., can be used alone or is applied in combination a variety of by a kind.
As oxime ester system Photoepolymerizationinitiater initiater, such as ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl)-can be enumerated 9H- carbazole -3- base] -, 1- (O- acetyl group oxime) etc..
In addition, benzoin, benzoin methyl ether, benzoin isopropyl can also be used as other Photoepolymerizationinitiater initiaters The benzoins such as base ether system Photoepolymerizationinitiater initiater, acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- benzene Base acetophenone, 1,1- ww-dichloroacetophenone, 1- hydroxycyclohexylphenylketone, 2- benzyl -2- dimethylamino -1- (4- morpholino benzene Base)-butanone-1,2- methyl-1-[4- (methyl thio)-2- phenyl) the equal aromatic ketones system photopolymerization of-2- morpholino-acetone-1 draws Send out agent, the anthraquinones such as 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone, 2- amyl anthraquinone, 2- amino anthraquinones It is Photoepolymerizationinitiater initiater, the ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal system Photoepolymerizationinitiater initiater, benzophenone, The benzophenone series light such as methyl benzophenone, 4,4 '-dichloro benzophenones, 4- benzoyl -4 '-methyldiphenyl sulfide are poly- Conjunction initiator, the acridine derivatives system Photoepolymerizationinitiater initiater such as bis- (9,9 '-acridinyl) heptane of 9- phenylacridine, 1,7-, 2,4,5- Imidazole dimer system Photoepolymerizationinitiater initiater of triarylimidazoles dimer or derivatives thereof etc..These substances can be used alone a kind Or it is applied in combination a variety of.
(content of (B) ingredient)
(B) content of ingredient is from obtaining what the linearity being capable of forming on the depth direction of corrosion-resisting pattern profile increased From the perspective of the photosensitive polymer combination of resist shape, on the basis of the solid component total amount of photosensitive polymer combination Meter is suitably selected from 0.2~15 mass %, 0.4~5 mass % or 0.6~1 mass %.In addition, (B) ingredient contains When amount is 0.2 mass % or more, exposure portion is difficult to dissolve out in development, when being 15 mass % or less, can inhibit heat resistance It reduces.
Photopolymerization sensitizer > of the < (C) containing benzophenone cpd
(C) the photopolymerization sensitizer of ingredient contains benzophenone cpd as essential component, can also be as needed by two Photopolymerization sensitizer other than benzophenone compound is applied in combination with benzophenone cpd.
Preferably there is benzophenone cpd as the essential component in (C) ingredient 1 or more to be gathered selected from display light The functional group of conjunction property, the alkyl amino such as amino, ethylamino, dimethylamino, diethylamino, dibutylamino, hydroxyl The benzophenone cpd of group in base, methoxyl group, ethyoxyl, butoxy and phenyl more preferably has 2 or more and is selected from The dialkyl amidos such as amino, dimethylamino, diethylamino, dibutylamino, hydroxyl, methoxyl group, ethyoxyl, butoxy and The benzophenone cpd of group in phenyl is further preferred that the hexichol first with 2 or more diethylaminos or hydroxyl Ketone compound, particularly preferably 4,4 '-bis- (diethylamino) benzophenone.(C) benzophenone cpd of ingredient can be single It solely uses a kind or is mixed with two or more.
As the benzophenone cpd of (C) ingredient, such as 4,4 '-diaminobenzophenones, 4 are preferably enumerated, 4 '- Bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (dibutylamino) hexichol first Ketone, 4- ethylamino benzophenone, 2,4 dihydroxyl benzophenone, 3,4- dihydroxy benaophenonel, 2,3,4- trihydroxy hexichol Ketone, 2,3,4,4 '-tetrahydroxybenzophenones, 2,2 ', 4,4 '-tetrahydroxybenzophenones, 2,2 ', 4,4 '-tetramethoxy hexichol Ketone, 2,2 ', 4,4 '-tetraethoxy benzophenone, 2,2 ', 4,4 '-four butoxy benzophenone, 2,2 '-dihydroxy -4,4 ' - Dimethoxy-benzophenone, 2,2 '--4,4 '-diethoxy benzophenone of dihydroxy, 2,2 '--4,4 '-dibutoxies of dihydroxy Benzophenone, 4,4 '-dihydroxy benaophenonels, 4,4 '-dimethoxy-benzophenones, 4,4 '-dibutoxy benzophenone, 4, 4 '-diphenylbenzophenones etc..These benzophenone cpds, which can be used alone, or to be applied in combination a variety of by a kind.
As the photopolymerization sensitizer being applied in combination with benzophenone cpd as needed as (C) ingredient, such as can Enumerate pyrazoline based compound, anthracene based compound, coumarin series compounds, xanthone based compound, thioxanthones based compound, Oxazole based compound, benzoxazoles based compound, thiazole compound, benzothiazole based compound, three azole compounds, 1,2- Talan based compound, triazine based compound, thiophene based compound, naphthalimide based compound, triaryl amine system Close object etc..Wherein, it is preferable to use thioxanthones based compound.The concrete example of photopolymerization sensitizer as thioxanthones based compound Son, such as thioxanthones, 2,4- diethyl thioxanthene-9-one, 2-isopropylthioxanthone, 2-chlorothioxanthone can be enumerated etc..
When using photopolymerization sensitizer other than these benzophenone cpds, these substances can be used alone a kind or Two or more is applied in combination.
(content of the benzophenone cpd as (C) ingredient)
The content of benzophenone cpd as (C) ingredient is with the solid component total amount in photosensitive polymer combination Benchmark meter, preferably from 0.001~20 mass %, more preferably from 0.01~10 mass %, further preferably from 0.01~ 2.0 mass %, it is particularly preferably suitably selected in the range of 0.01~0.1 mass %.For 0.001 mass % or more When, have the tendency that being easier to take into account directly retouching type exposure machine and projection exposure machine when being 20 mass % or less, there is good cross sectional shape Formation become the tendency being more easier.
(content of the photopolymerization sensitizer other than benzophenone cpd)
Cooperating the Photoepolymerizationinitiater initiater that can be used as (C) ingredient and use also according to needs other than benzophenone cpd When, content is counted on the basis of the solid component total amount in photosensitive polymer combination, preferably from 0.001~1 mass %, more Preferably suitably selected from 0.005~0.5 mass %, further preferably in the range of 0.01~0.1 mass %.For When 0.001 mass % or more, have the tendency that being easier to take into account directly retouching type exposure machine and projection exposure machine, when being 1 mass % or less, Have the tendency that being easier to obtain good cross sectional shape.
(content of (C) ingredient entirety)
Cooperating the Photoepolymerizationinitiater initiater that can be used as (C) ingredient and use also according to needs other than benzophenone cpd When, the content of whole photopolymerization sensitizers joined together is counted on the basis of the solid component total amount in photosensitive polymer combination, Preferably from 0.002~21 mass %, more preferably from 0.005~10 mass %, further preferably from 0.005~1 matter It measures %, particularly preferably suitably selected from the range of 0.01~0.5 mass %.When for 0.002 mass % or more, have more The straight tendency for retouching type exposure machine and projection exposure machine is easily taken into account to be easier to obtain good section shape when being 21 mass % or less The tendency of shape.
< (D) photopolymerizable compound >
(D) as long as ingredient has the functional group of display optical polymerism, such as vinyl, allyl, propargyl, butylene The ethylenic bonds such as base, acetenyl, phenylene-ethynylene, dimaleoyl imino, nadikimide base, (methyl) acryloyl group are unsaturated The compound of group, then be not particularly limited, from the viewpoint of reactivity, preferably with the chemical combination of (methyl) acryloyl group Object.
In addition, (methyl) acryloyl group refers to acryloyl group or methylacryloyl in this specification, (methyl) acrylic acid Ester refers to acrylate or methacrylate.
As (D) ingredient, such as preferably enumerate (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxyl Propyl ester etc. (methyl) hydroxyalkyl acrylates class, the list of glycol or two such as ethylene glycol, methoxyl group tetraethylene glycol, polyethylene glycol (methyl) esters of acrylic acid, N, (methyl) propylene such as N- dimethyl (methyl) acrylamide, N- methylol (methyl) acrylamide Amides, (methyl) the acrylate class such as (methyl) acrylic acid N, N- dimethylamino ethyl ester, hexylene glycol, three hydroxyl first The polyalcohols such as base propane, pentaerythrite, two (trimethylolpropanes), dipentaerythritol, trihydroxy ethyl isocyanurate or it Ethylene oxide or propylene oxide adduct polynary (methyl) esters of acrylic acid, it is (methyl) phenoxyethyl acrylate, double The ethylene oxide of the phenols such as polyethoxy two (methyl) acrylate of phenol A or (methyl) acrylate of propylene oxide adduct Class, diglycidyl ether, trimethylolpropane tris glycidyl ether, triglycidyl group isocyanuric acid ester etc. shrink (methyl) esters of acrylic acid and melamine (methyl) acrylate of glyceryl ether etc..These (D) ingredients can be used alone Or it is applied in combination a variety of.
Furthermore it is also possible to polynary (methyl) containing above-mentioned polyalcohol or their ethylene oxide or propylene oxide adduct Esters of acrylic acid.
(content of (D) ingredient)
(D) content of ingredient is counted on the basis of the solid component total amount in photosensitive polymer combination, preferably from 2~50 Quality %, the more preferably suitably selection from 3~20 mass %, further preferably from 3~10 mass %.For 2 matter When measuring % or more, since photo sensitivity is low, the tendency that exposure portion can be inhibited to dissolve out in development is 50 mass % or less When, the reduction of heat resistance can be inhibited.
< (E) pigment >
In the photosensitive polymer combination of present embodiment, it can according to need further with the use of (E) pigment.(E) Ingredient preferably according in masking wiring etc. required color carry out using.As (E) ingredient, face needed for appropriate selection is shown The colorant of color carries out use, such as preferably enumerates green phthalocyanine blue, phthalocyanine green, iodine, dual-azo yellow, crystal violet, oxygen Change titanium, carbon black, naphthalene it is black etc. well known to colorant.
(content of (E) ingredient)
When using (E) ingredient, the content of (E) ingredient is from the viewpoint of further masking wiring, with photoresist group It closes and counts on the basis of the solid component total amount in object, preferably from 0.1~5 mass %, more preferably from 0.1~3 mass %, into one Step suitably selects preferably from 0.5~2 mass %.
< (F) inorganic filler >
It, can be in order to improve many characteristics such as adaptation, hardness of film in the photosensitive polymer combination of present embodiment (F) inorganic filler is further used as needed.
As (F) ingredient, silica (SiO can be used for example2), aluminium oxide (Al2O3), zirconium oxide (ZrO2), talcum (3MgO·4SiO2·H2O), aluminium hydroxide (Al (OH)3), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4)、 Zinc oxide (ZnO), magnesium titanate (MgOTiO2), carbon (C) etc..These inorganic fillers can be used alone or be applied in combination more Kind.
(F) average grain diameter of ingredient preferably from 0.1~20 μm, more preferably from 0.1~10 μm, further preferably from 0.1~5 μm, the still more preferably suitably selection from 0.1~1 μm.It, can be into one when average grain diameter is 20 μm or less Step inhibits the reduction of insulating reliability.Here, the average grain diameter of (F) ingredient is using utilization dynamic light scattering formula Nanotrac Degree distribution meter " UPA-EX150 " (Nikkiso Company Limited's system) and laser diffraction and scattering formula Microtrac particle size distribution meter " MT- The value of 3100 " (Nikkiso Company Limited's systems) measurement.
(F) in ingredient, from the viewpoint of it can be improved heat resistance, silica is preferably comprised, is brazed from can be improved The sight of the adhesive strength of underfill and cured film after heat resistance, resistance to cracking (thermal shock resistance) and resistance to PCT test Point sets out, and preferably comprises barium sulfate, can also combine containing silica and barium sulfate.In addition, inorganic filler is from can mention From the perspective of high anti-flocculating result, can suitably selection aluminium oxide or organosilan based compound carried out surface treatment Inorganic filler.
Aluminium in the surface for the inorganic filler being surface-treated using aluminium oxide or organosilan based compound Element composition is preferably from 0.5~10 atom %, more preferably from 1~5 atom %, further preferably from 1.5~3.5 originals It is suitably selected in sub- %.In addition, in the surface for the inorganic filler being surface-treated with organosilan based compound Silicon element composition preferably from 0.5~10 atom %, more preferably from 1~5 atom %, further preferably from 1.5~ It is suitably selected in 3.5 atom %.In addition, the table for the inorganic filler being surface-treated with organosilan based compound Carbon in face element composition preferably from 10~30 atom %, more preferably from 15~25 atom %, further preferably from It is suitably selected in 18~23 atom %.These elements composition can be used XPS and be measured.
As the inorganic filler being surface-treated with aluminium oxide or organosilan based compound, such as use aluminium oxide Or the barium sulfate that organosilan based compound is surface-treated can be used as NanoFine BFN40DC (Japanese Solvay plants of formula Commercial firm's system, trade name) it buys.
(content of (F) ingredient)
Use (F) ingredient when, content is counted on the basis of the solid component total amount of photosensitive polymer combination, preferably from 10~80 mass %, more preferably from 15~70 mass %, further preferably from 20~50 mass %, further preferably from It is suitably selected in 25~40 mass %.When in above range, consolidating for photosensitive polymer combination can be further improved Compound intensity, heat resistance, insulating reliability, thermal shock resistance, resolution ratio etc..
The content of silica when using silica as (F) ingredient is with the solid component of photosensitive polymer combination It is counted on the basis of total amount, preferably from 5~60 mass %, more preferably from 15~55 mass %, further preferably from 15~50 It is suitably selected in quality %.In addition, the content of barium sulfate when using barium sulfate as (F) ingredient is with photoresist group Close object solid component total amount on the basis of count, preferably from 5~30 mass %, more preferably from 5~25 mass %, further it is excellent Selection of land is suitably selected from 5~20 mass %.When in above range, soldering heat resistance and resistance to can be further improved The adhesive strength of underfill and cured film after PCT test.
< diluent >
The photosensitive polymer combination of present embodiment can according to need using diluent.As diluent, such as can To use organic solvent etc..As organic solvent, such as the ketones such as methyl ethyl ketone, cyclohexanone can be enumerated, toluene, dimethylbenzene, tetramethyl Base benzene etc. is aromatic hydrocarbon, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, The glycol ethers such as dihydroxypropane single-ethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, acetic acid fourth The esters such as ester, butyl cellosolve acetate, carbitol acetate, the aliphatic hydrocarbons such as octane, decane, petroleum ether, naphtha, hydrogen Petroleum series solvent such as naphtha, solvent naphtha etc..
The usage amount of diluent is preferably reached from the content of the solid component total amount made in photosensitive polymer combination 50~90 mass %, 60~80 mass % are more preferably up to, further preferably reach appropriate in the amount of 65~75 mass % Selection.That is, the content of the diluent in photosensitive polymer combination when using diluent is preferably from 10~50 matter Measure %, the more preferably suitably selection from 20~40 mass %, further preferably from 25~35 mass %.By being upper It states in range, the coating raising of photosensitive polymer combination, the pattern that more fine can be formed.
< (G) curing agent >
The photosensitive polymer combination of present embodiment can also contain (G) curing agent as needed.It, can as (G) ingredient Its own compound being cured by heat, ultraviolet light etc. is enumerated, or passes through heat, ultraviolet light etc. and present embodiment The carboxyl, hydroxyl of (A) ingredient as photo-curable ingredient in photosensitive polymer combination react and cured chemical combination Object.By using curing agent, heat resistance, adaptation, chemical reagent resistance of final cured film etc. can be improved.
Epoxide, melamine compound, evil can be enumerated as (G) ingredient, such as Thermocurable compound Isoxazoline compound etc..As epoxide, such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenation pair can be enumerated Phenol A type epoxy resin, brominated bisphenol a type epoxy resin, phenolic resin varnish type epoxy resin, bisphenol-s epoxy resin, biphenyl type ring The hetero ring types such as oxygen resin or triglycidyl group isocyanuric acid ester epoxy resin, bis-xylene phenol-type epoxy resin etc..
As melamine compound, such as triamido triazine, hexa methoxy melamine, six butoxylated three can be enumerated Poly cyanamid etc..Wherein, from the viewpoint of the heat resistance for further increasing cured film, epoxide (asphalt mixtures modified by epoxy resin is preferably comprised Rouge), more preferably epoxide and blocked isocyanate are used in combination.
As blocked isocyanate, polyisocyanate compounds and isocyanate-terminated dose of addition reaction can be used to produce Object.As the polyisocyanate compounds, such as first phenylene diisocyanate, penylene diformazan group diisocyanate, benzene can be enumerated Support diisocyanate, naphthylene diisocyanate, bis- (isocyanatomethyl) hexamethylenes, tetramethylene diisocyanate, six methylenes Group diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate etc. are poly- Isocyanate compound and their adduct, biuret object and isocyanuric acid ester object etc..
(G) ingredient can be used alone or be applied in combination and is a variety of.When using (G) ingredient, content is with photoresist group Close object solid component total amount on the basis of count, preferably from 2~40 mass %, more preferably from 3~30 mass %, further it is excellent Selection of land is suitably used from 5~20 mass %.It, can be while maintaining excellent developing, into one by in above range Step improves the heat resistance for being formed by cured film.
< (H) epoxy curing agent >
In addition, in the photosensitive polymer combination of present embodiment, according to need in order to further increasing final solidification (H) epoxy curing agent can be used together in many characteristics such as heat resistance, adaptation, the chemical reagent resistance of film.
The specific example of epoxy curing agent as this (H) ingredient, such as 2-methylimidazole, 2- second can be enumerated The imidazoles such as base -4-methylimidazole, 1 benzyl 2 methyl imidazole, 2- phenylimidazole, 2- phenyl -4- methyl -5- hydroxymethylimidazole Derivative: the guanamines such as acetylguanamine, benzoguanamine: diaminodiphenyl-methane, m-phenylene diamine (MPD), m-xylene diamine, diamino The polyamines classes such as base diphenyl sulfone, dicyandiamide, urea, urea derivative, melamine, polynary hydrazides: their acylate or Epoxy adduct: the amine complex of boron trifluoride: ethyl diamino-S- triazine, 2,4- diamino-S- triazine, 2,4- diamino- Triazine derivatives species such as 6- xylyl-S- triazine etc..
Epoxy curing agent as (H) ingredient may be used singly or in combin it is a variety of, in use, photonasty The content of epoxy curing agent in resin combination is from the viewpoint of reliability improve, with photosensitive polymer combination It counts on the basis of solid component total amount, is preferably suitably selected from 0.1~10 mass % from 0.01~20 mass %, more preferably .
< (I) elastomer >
The photosensitive polymer combination of present embodiment can contain (I) elastomer.(I) ingredient can especially incite somebody to action this It is preferably used when the photosensitive polymer combination of embodiment is in conductor package substrate.Pass through addition (I) ingredient, energy Flexibility, adhesive strength caused by enough deformations (internal stress) inhibited inside resin caused by the cure shrinkage because of (A) ingredient Reduction.That is, can be improved the flexibility of the cured film formed by photosensitive polymer combination, adhesive strength etc..
As (I) ingredient, for example, can enumerate styrene series elastomer, olefin-based elastomer, carbamate based elastomers, Polyester-based elastomer, polyamide-based elastomer, acrylic elastomer and organic silicon-type elastomer etc..These elastomers are by hard chain Segment components and soft segment component are formed, and in general, the former facilitates heat resistance and intensity, the latter facilitate flexibility and tough Property.
Carbamate based elastomers are formed by hard segment by low molecular two pure and mild diisocyanate and macromolecule is (long Chain) two pure and mild diisocyanate are formed by the structural unit of soft chain segment and are formed, the concrete example as macromolecule (long-chain) glycol Son can enumerate polypropylene glycol, poly- tetrahydrofuran, poly- (adipic acid 1,4-butanediol ester), poly- (adipic acid-ethyl alcohol-Isosorbide-5-Nitrae-fourth two Alcohol ester), polycaprolactone, poly- (carbonic acid 1,6-HD ester), poly- (adipic acid 1,6-HD-neopentyl glycol ester) etc..
The number-average molecular weight of macromolecule (long-chain) glycol is preferably 500~10,000.Other than ethylene glycol, it can also make With short-chain diols such as propylene glycol, 1,4-butanediol, bisphenol-As, the number-average molecular weight of short-chain diol is preferably 48~500.As ammonia The specific example of carbamate elastomer is commercially available PANDEX T-2185, T-2983N (Dainippon Ink Chemicals's system), シ ラ Network ト ラ Application E790 etc..
As polyester-based elastomer, for example, can enumerate by dicarboxylic acids or derivatives thereof and diol compound or derivatives thereof into Row polycondensation and the substance obtained.As the specific example of dicarboxylic acids, terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid can be enumerated The hydrogen atom of equal aromatic dicarboxylic acids and their aromatic proton by methyl, ethyl, phenyl etc. instead of aromatic dicarboxylic acid, oneself The ester ring types two such as aliphatic dicarboxylic acid and cyclohexane dicarboxylic acid that the carbon numbers such as diacid, decanedioic acid, dodecanedicarboxylic acid are 2~20 Carboxylic acid etc..
These compounds can be used alone or be applied in combination a variety of.
As the specific example of diol compound, can enumerate ethylene glycol, 1,3-PD, 1,4-butanediol, 1,6- oneself two Binary shown in the aliphatic diols such as alcohol, 1,10- decanediol, 1,4- cyclohexanediol and ester ring type glycol or the following general formula (VI) Phenol etc..
[chemical formula number 12]
In logical formula (VI), Y indicates the cycloalkylidene that the alkylidene that carbon number is 1~10, carbon number are 4~8, is selected from-O- ,-S- And-SO2In divalent functional groups or phenyl ring between be directly bonded, R1And R2It is former to each independently represent hydrogen atom, halogen The alkyl that son or carbon number are 1~12, l and m each independently represent 0~4 integer, and p indicates 0 or 1.Alkylidene, cycloalkylidene It can be straight-chain and be also possible to branched, it can also be by halogen atom, alkyl, aryl, aralkyl, amino, amide groups, alkoxy Deng substitution.
It is sub as its concrete example as dihydric phenol shown in logical formula (VI), bisphenol-A, bis- (4- hydroxy phenyl) first can be enumerated Alkane, bis- (4- hydroxy-3-methyl phenyl) propane, resorcinols etc..These compounds can be used alone or be applied in combination a variety of.
Furthermore it is also possible to using make aromatic polyester (such as polybutylene terephthalate (PBT)) partially for hard segment at Dividing, making aliphatic polyester (such as polytetramethylene glycol) partially is segmented copolymer obtained from soft segment component.According to The type of hard segment and soft chain segment, ratio, the difference of molecular weight, there is various grades.Specifically, being commercially available Hytrel (DU PONT-TORAY Co. Ltd. system, " Hytrel " be registered trademark), Pelprene (Japan spin Co. Ltd. system, " Pelprene " is registered trademark), ESPEL (Hitachi Chemical Co., Ltd.'s system, " ESPEL " they are registered trademark) etc..
As acrylic elastomer, such as can enumerate with ethyl acrylate, butyl acrylate, methoxyethyl second The substance that the acrylate such as ester, ethoxyethyl acrylate are synthesized as principal component.It, can be in addition, as crosslinking points monomer Use methyl propenoic acid glycidyl base ester, allyl glycidyl ether etc..Furthermore it is also possible to further copolymerized acrylonitrile or Ethylene.Specifically, can for example enumerate acrylonitrile-butylacrylate copolymer, acrylonitrile-butylacrylate-ethyl acrylate Copolymer, acrylonitrile-butylacrylate-methyl propenoic acid glycidyl base ester copolymer etc..
In addition, rubber-modified epoxy resin can also be used other than above-mentioned thermoplastic elastomer (TPE).Change through rubber Property epoxy resin for example can by using two terminal carboxylic's modified version butadiene-propylene nitrile rubbers, terminal amino group modification have Machine silicon rubber etc. is to above-mentioned bisphenol f type epoxy resin, bisphenol A type epoxy resin, salicylide type epoxy resin, phenol novolacs Part or all of epoxy group of type epoxy resin or cresol novolak type epoxy resin is modified to obtain.These elasticity In body, from the viewpoint of shear bond, preferably two terminal carboxyl group modified butadienes-acrylonitrile copolymer, with hydroxyl The ESPEL (Hitachi Chemical Co., Ltd.'s system, trade name: ESPEL1612,1620) of polyester-based elastomer.
When using (I) ingredient, content is relative to 100 mass parts of (A) ingredient (solid component), preferably from 2~40 matter Measure part, more preferably from 4~30 mass parts, further preferably from 10~25 mass parts, still more preferably from 15~22 It is suitably selected in mass parts.By in above range, spring rate of the cured film under high-temperature area becomes lower, and not Exposure portion is easier to dissolve out in developer solution.
The other additive > of <
In the photosensitive polymer combination of present embodiment, quinhydrones, methylnaphthohydroquinone, quinhydrones list first can be also used as needed The polymerization inhibitors such as base ether, catechol, pyrogallol, the tackifier such as bentonite, montmorillonite, organic silicon-type, fluorine system, vinylite system Defoaming agent, usual various additives known in silane coupling agent etc..In turn, the modified bromine of brominated epoxy compound, acid can be used Change the phosphate compound of epoxide, antimonial and phosphorus series compound, aromatic condensation phosphate, contain halogen condensation The fire retardants such as phosphate.
In addition, the photosensitive polymer combination of present embodiment can also be further as needed using melamine etc. (I) triaizine compounds are as closely sealed imparting agent.
The photosensitive polymer combination of present embodiment can by using roller mill, ball mill etc. to gradation composition equably It is kneaded, mixed to obtain.
[dry film]
The dry film of present embodiment has carrier film and has used the sense of the photosensitive polymer combination of present embodiment Photosphere.
The thickness of photosensitive layer is not particularly limited, preferably from 10~50 μm, more preferably from 15~40 μm, further it is excellent Selection of land is suitably selected from 20~30 μm.
The dry film of present embodiment can for example manufacture as follows: be coated with using reversed rolling method, intaglio plate rolling method, comma The photosensitive polymer combination of present embodiment is coated and is done on carrier film by method well known to method, curtain coating processes etc. It is dry, photosensitive layer is formed, to manufacture.
As carrier film, the polyester such as polyethylene terephthalate, polybutylene terephthalate (PBT), poly- third can be enumerated Polyolefin such as alkene, polyethylene etc..The thickness of carrier film is not particularly limited, and is preferably suitably selected from 5~100 μm of range .In addition, the dry film of present embodiment can also be on the face for the face opposite side of photosensitive layer being in contact with carrier film Protective layer is laminated.As protective layer, polymer films such as polyethylene, polypropylene etc. can be used for example.Furthermore it is also possible to using with The identical polymer film of above-mentioned carrier film, also can be used different polymer films.
The drying of film can be used using heated-air drying or the drying machine of far infrared or near infrared ray etc., as drying Temperature, for example, preferably from 60~120 DEG C, more preferably from 70~110 DEG C, further preferably from 80~100 DEG C it is appropriate Selection.In addition, as drying time, for example, preferably from 1~60 minute, more preferably from 2~30 minutes, it is further excellent Selection of land is suitably selected from 5~20 minutes.
[printed wiring board]
The printed wiring board of present embodiment has permanently to be covered by what the photosensitive polymer combination of present embodiment was formed Mould resist.
The printed wiring board of present embodiment is formed forever due to the photosensitive polymer combination for having by present embodiment Long mask resist, therefore the missing of undercutting or resist top that bottom is cut out will not occur, corrosion-resisting pattern section The line width of middle part (central portion) and most deep (bottom) on depth direction is not more than the line width of surface element, therefore has figure Linearity on the depth direction of case profile (end) is good, cross sectional shape is excellent, the corrosion-resisting pattern of excellent in resolution.In addition, The permanent mask resist has the miniaturization with electronic equipment in recent years or the aperture (opening through miniaturizeing of high performance Diameter) spacing between size and hole formation excellent in stability corrosion-resisting pattern.
[manufacturing method of printed wiring board]
The manufacturing method of the printed wiring board of present embodiment successively has following processes: this embodiment party is used on substrate The photosensitive polymer combination of formula or the dry film of present embodiment are arranged the process of photosensitive layer；It is formed using the photosensitive layer anti- The process of corrosion figure case；And the process that the corrosion-resisting pattern is solidified to form permanent mask resist.
Specifically, can for example manufacture as follows.
Firstly, using silk screen print method, spray-on process, rolling method, curtain on the metal depositions multilayer board such as copper facing plywood The methods of formula rubbing method, electrostatic covering with paint method with for example from 10~200 μm, preferably from 15~150 μm, more preferably from 20~ 100 μm, the film thickness further preferably suitably selected from 23~50 μm carry out photosensitive resin coating composition, then preferably exist By dried coating film at 60~110 DEG C, or the dry film progress using laminating machine to the present embodiment after having removed protective film Heat lamination, so that photosensitive layer be arranged on substrate.
Then, negative film is made directly to contact (or non-contact across the transparent film such as carrier film) in the photosensitive layer, with for example From 10~2,000mJ/cm2, preferably from 100~1,500mJ/cm2, more preferably from 300~1,000mJ/cm2In suitably select Unexposed portion is dissolved using dilute alkaline aqueous solution later and removes (development) by the exposure activity light selected, and forms resist pattern Case.As used active light, electron beam, ultraviolet light, X-ray etc., preferably ultraviolet light can be enumerated.In addition, as light source, it can To use low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, halogen lamp etc..
Then, by least one of post-exposure (ultraviolet exposure) and rear heating processing, make the exposure of the photosensitive layer Part sufficiently solidification, forms permanent mask resist.
The light exposure of post-exposure is preferably from 100~5,000mJ/cm2, more preferably from 500~2,000mJ/cm2, into one Step is preferably from 700~1,500J/cm2In suitably select.
The heating temperature heated afterwards preferably from 100~200 DEG C, more preferably from 120~180 DEG C, further preferably It is suitably selected from 135~165 DEG C.
The heating time heated afterwards preferably from 5 minutes~12 hours, more preferably from 10 minutes~6 hours, further It is suitably selected preferably from 30 minutes~2 hours.
The permanent mask resist being thusly-formed from the viewpoint of insulating properties or resolution ratio, thickness be preferably 10 μm with Above, more preferably 10~100 μm, further preferably 10~50 μm.
Later, wiring is formed using etching, makes printed wiring board.
Embodiment
More specifically illustrate the purpose and advantage of present embodiment, but this embodiment party below according to Examples and Comparative Examples Formula does not limit embodiment below.
(synthesis example 1)
Adding bisphenol F phenolic type epoxy resin (a), (EXA-7376, Dainippon Ink Chemicals's system contain in logical formula (II) Y3And Y4For glycidyl, R12For bisphenol F phenolic type epoxy resin, the epoxide equivalent of the structural unit of hydrogen atom: 186) 350 mass parts, 70 mass parts of acrylic acid (b), 0.5 mass parts of methylnaphthohydroquinone, 120 mass parts of carbitol acetate, heating It to 90 DEG C and is stirred, to make its reaction, dissolves mixture fully.Then, acquired solution is cooled to 60 DEG C, added Add 2 mass parts of triphenylphosphine, be heated to 100 DEG C, makes its reaction until the acid value of solution reaches 1mgKOH/g hereinafter, being contained The solution of (A1 ') ingredient.Tetrahydro phthalate anhydride (THPAC) (c) 98 mass parts and carbitol are added in solution after the reaction 85 mass parts of acetate, are heated to 80 DEG C, react it 6 hours.Later, it is cooled to room temperature, the concentration for obtaining solid component is The THPAC modified bisphenol F nobolak type epoxy acrylate (epoxy resin (1)) as (A1) ingredient of 73 mass %.
(synthesis example 2)
Bisphenol f type epoxy resin is added in the flask for having blender, reflux cooler and thermometer (containing general formula (IV) Y in6For glycidyl, R14For the bisphenol F phenolic type epoxy resin of the structural unit of hydrogen atom) (a) (epoxy is worked as Amount: 526) 1,052 mass parts, 144 mass parts of acrylic acid (b), 1 mass parts of methylnaphthohydroquinone, 850 mass parts of carbitol acetate and 100 mass parts of solvent naphtha, heating stirring is carried out at 70 DEG C, mixture is dissolved.Then, solution is cooled to 50 DEG C, 2 mass parts of triphenylphosphine, 75 mass parts of solvent naphtha are added, are heated to 100 DEG C, make its reaction until solid component acid value reaches To 1mgKOH/g hereinafter, being contained the solution of (A2 ') ingredient.Then, acquired solution is cooled to 50 DEG C, puts into tetrahydro benzene two 745 mass parts of formic anhydride (THPAC) (c), 75 mass parts of 75 mass parts of carbitol acetate and solvent naphtha, are heated to 80 DEG C, react it 6 hours.Later, it is cooled to room temperature, acquisition solid component acid value is 80mgKOH/g, solid component is 62 matter Measure the THPAC modified bisphenol F type epoxy acrylate (epoxy resin (2)) as (A2) ingredient of %.
(Examples 1 to 9, the Comparative Examples 1 to 5)
Complexing compositions are combined into according to matching shown in table 1, is kneaded using 3 roller mills, prepares photoresist Composition.Addition carbitol acetate is until solid component concentration reaches 70 mass %, acquisition photosensitive polymer combination.
Table 1
* the numerical value in table is the value of the mass parts of solid component used in the preparation of photosensitive polymer combination
In addition, the details of each material in table 1 is as follows.
Epoxy resin (1)~(3) are the epoxy resin (1) containing sour modified vinyl obtained in synthesis example 1~3 respectively ~(3).
Irgacure 907:2- methyl-[4- (methyl thio) phenyl] morpholino -1- acetone (BASF AG's system, commodity Name)
Irgacure 819: bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides (BASF AG's system, trade name)
Irgacure 369:2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-(BASF AG of butanone -1 System, trade name)
Irgacure OXE02: ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl group oxime) (BASF AG's system, trade name)
Irgacure TPO:2,4,6- trimethylbenzoy-dipheny-phosphine oxide (BASF AG's system, trade name)
DETX:DETX-S, 2,4- diethyl thioxanthone (Nippon Kayaku K. K's system, trade name)
The bis- diethylamino benzophenone of EAB:4,4 '-(HODOGAYA CHEMICAL CO., LTD. system, trade name)
DPHA: dipentaerythritol hexaacrylate (Nippon Kayaku K. K's system, trade name)
Phthualocyanine pigment: phthualocyanine pigment (Sanyo Color Works's system)
B34: barium sulfate particles (Sakai Chemical Industry Co., Ltd.'s system, trade name, average grain diameter: 0.3 μm)
SFP20M: silicon dioxide granule (Deuki Kagaku Kogyo Co., Ltd, trade name, average grain diameter: 0.3 μm)
Curing agent: YX4000X (Mitsubishi chemical Co., Ltd's system, trade name, biphenyl type epoxy resin)
Melamine: Nissan Chemical Ind Ltd's system
Then, using the photosensitive polymer combination of above-mentioned acquisition, each evaluation is carried out under the conditions of shown in following.It will comment Valence result is shown in Table 2.
[the production method I of test film]
The photosensitive polymer combination of Examples and Comparative Examples is reached according to the film thickness after drying using silk screen print method After 35 μm of mode is coated on the copper facing multilayer board (MCL-E-67, Hitachi Chemical Co., Ltd.'s system) with a thickness of 0.6mm, It is 20 minutes dry using hot air circulation type drying machine at 80 DEG C.Then, make have predetermined pattern (in 50 μm of aperture and hole Distance is 50 μm of pattern in the heart) negative mask it is closely sealed on film, using projection ultraviolet exposure apparatus according with 100mJ/cm2 Light exposure be exposed.Later, using the aqueous sodium carbonate of 1 mass % with 60 seconds, 1.765 × 105The pressure of Pa carries out Spray development carries out dissolution development to unexposed portion.Then, using ultraviolet exposure apparatus according, with 1000mJ/cm2Light exposure It is exposed, is heated 1 hour at 150 DEG C, make the test film with permanent mask resist.
[the production method II of test film]
The photosensitive polymer combination of Examples and Comparative Examples is reached according to the film thickness after drying using silk screen print method After 35 μm of mode is coated on the copper facing multilayer board (MCL-E-67, Hitachi Chemical Co., Ltd.'s system) with a thickness of 0.6mm, It is 20 minutes dry using hot air circulation type drying machine at 80 DEG C.Then, make have predetermined pattern (in 50 μm of aperture and hole Distance is 50 μm of pattern in the heart) negative mask it is closely sealed on film, using direct-writing ultraviolet exposure apparatus according with 100mJ/cm2 Light exposure be exposed.Later, using the aqueous sodium carbonate of 1 mass % with 60 seconds, 1.765 × 105The pressure of Pa carries out Spray development carries out dissolution development to unexposed portion.Then, using ultraviolet exposure apparatus according, with 1000mJ/cm2Light exposure It is exposed, is heated 1 hour at 150 DEG C, make the test film with permanent mask resist.
[resolution ratio I]
By the test film made by above-mentioned production method I epoxy resin ((Epoxy plants of formulas of Japan of Epikote 828 Commercial firm's system, trade name) in use triethylene tetramine as curing agent) injection molding and after curing sufficiently, utilize grinder (REFINE-POLISHER (Refinetec Co. Ltd. system)) is ground, and the section of pattern is cut out, metal microstructure is utilized Sem observation resist shape.Judged by following standard.
A: resist shape does not confirm the missing of undercutting, resist top, and on the depth direction of pattern contour Linear is good (referring to Fig.1).
B: resist shape confirms the missing of undercutting, resist top, and straight on the depth direction of pattern contour Linear poor (referring to Fig. 2).
[resolution ratio II]
By the test film made by above-mentioned production method II with ((Epoxy plants of Japan of Epikote 828 of epoxy resin Formula commercial firm system, trade name) in use triethylene tetramine as curing agent) injection molding and after curing sufficiently, utilize grinder (REFINE-POLISHER (Refinetec Co. Ltd. system)) is ground, and the section of pattern is cut out, metal microstructure is utilized Sem observation resist shape.Judged by following standard.
A: resist shape does not confirm the missing of undercutting, resist top, and on the depth direction of pattern contour Linear is good (referring to Fig.1).
B: resist shape confirms the missing of undercutting, resist top, and straight on the depth direction of pattern contour Linear poor (referring to Fig. 2).
[adaptation]
Using silk screen print method according to the film after drying on the copper foil (Nippon Denkai, Ltd.'s system) with a thickness of 35 μm After thickness reaches 35 μm of mode coating Examples and the photosensitive polymer combination of comparative example, hot air circulation is used at 80 DEG C Formula drying machine is 20 minutes dry.Then, make above-mentioned negative mask closely sealed on film, use direct-writing exposure machine (ORC Co., Ltd. System, trade name: EDi-5008) with 100mJ/cm2Light exposure photosensitive layer is exposed.Later, the carbonic acid of 1 mass % is utilized Sodium water solution was with 60 seconds, 1.765 × 105The pressure of Pa carries out spray development, carries out dissolution development to unexposed portion.Then, make With ultraviolet exposure apparatus according, with 1000mJ/cm2Light exposure be exposed, heat 1 hour, be produced on copper foil at 150 DEG C Test film equipped with permanent mask resist.Make institute using bonding agent (Nichiban Co. Ltd. system, trade name: Araldite) The face equipped with permanent mask resist for obtaining test film is consolidated with copper facing plywood (MCL-E-67, Hitachi Chemical Co., Ltd.'s system) Change, bonding.
After placing 12 hours, one end of copper foil is peeled off into 10mm.Then, fixed plywood, using fixture by the copper of stripping Foil is clamped, and is measured and is shelled on 8 thickness directions (vertical direction) in copper foil with 50mm/ minutes tensile speeds, at room temperature From when load (peel strength), calculate average value, index as adhesive strength by 8 measured values.In addition, peel strength Evaluation according to JIS C 5016 (peel strength of 1994- conductor) carry out, evaluated by following standard.In addition, this explanation Room temperature indicates 25 DEG C in book.
A: peel strength is greater than 0.5kN/mm.
B: peel strength is the range of 0.3~0.5kN/mm.
C: peel strength is less than 0.3kN/mm.
[insulating properties (electrical insulating property)]
Instead of copper facing multilayer board, the bismaleimide for being formed with comb type electrode (line/interval=10 μm/10 μm) is used In addition to this amine triazine substrate is identically formed test film with method documented by above-mentioned [the production method II of test film], will It is exposed to 135 DEG C, 85%, under the conditions of 5V.Later, the degree occurred using 100 times of metal microstructure sem observation migration, according to Following standard is evaluated.
A: even if more than 200 hours, in the case where will not migrating in permanent mask resist, resistance value do not have yet It is reduced to 10-6Ω or less.
B:, will not there is a situation where migrate in permanent mask resist when at 100 hours or more and less than 200 hours Under, resistance value be not also reduced to 10-6Ω or less.
C: when less than 100 hours, migration occurs in permanent mask resist, resistance value is reduced to 10-6Ω or less.
[soldering heat resistance]
Water-soluble using being coated on the test film made same as the method that above-mentioned [the production method II of test film] is recorded Property solder flux, impregnates 10 seconds in 265 DEG C of solder slots.It is recycled this as 1, repeatedly after 6 circulations, visually observation is permanent The appearance of mask resist is evaluated according to standard below.
3: having no cosmetic variation in permanent mask resist 30cm × 30cm.
2: floating or being bubbled for 1~5 film having occurred in permanent mask resist 30cm × 30cm.
1: floating or being bubbled for 6 or more films having occurred in permanent mask resist 30cm × 30cm.
[resistance to cracking]
By -65 DEG C of 30 minutes/(room temperature；25 DEG C)/150 DEG C of conducts in 30 minutes, 1 circulation, it will be with the above-mentioned [system of test film Make method II] test film that equally makes of method recorded after 1000 circulations, visually observes permanent mask resist repeatedly Appearance is evaluated according to following standard.
3: having no cosmetic variation in permanent mask resist 30cm × 30cm.
2: floating or being bubbled for 1~5 film having occurred in permanent mask resist 30cm × 30cm.
1: floating or being bubbled for 6 or more films having occurred in permanent mask resist 30cm × 30cm.
[solvent resistance]
By the same test film made of the method recorded with above-mentioned [the production method II of test film] at room temperature (25 DEG C, It is same below) it is immersed in isopropanol 30 minutes, whether after confirming the appearance of permanent mask resist without exception, utilization is transparent Adhesive tape carries out disbonded test.
3: the appearance of permanent mask resist is not without exception, peeling-off.
2: the appearance of permanent mask resist varies slightly.
1: the appearance of permanent mask resist has abnormal or peeling-off.
[acid resistance]
The same test film made of the method recorded with above-mentioned [the production method II of test film] is immersed at room temperature 30 minutes in 10 mass % aqueous hydrochloric acid solutions, after confirming the appearance of permanent mask resist whether without exception, transparent adhesive tape is utilized Band carries out disbonded test.
3: the appearance of permanent mask resist is not without exception, peeling-off.
2: the appearance of permanent mask resist varies slightly.
1: the appearance of permanent mask resist has abnormal or peeling-off.
[alkali resistance]
The same test film made of the method recorded with above-mentioned [the production method II of test film] is immersed in 5 at room temperature 30 minutes in quality % sodium hydrate aqueous solution, whether after confirming the appearance of permanent mask resist without exception, utilization is transparent Adhesive tape carries out disbonded test.
3: the appearance of permanent mask resist is not without exception, peeling-off.
2: the appearance of permanent mask resist varies slightly.
1: the appearance of permanent mask resist has abnormal or peeling-off.
Table 2
As shown in table 2, this embodiment party of the Examples 1 to 9 of benzophenone cpd has been used as photopolymerization sensitizer No matter the photosensitive polymer combination of formula uses any one of projection exposure device and direct-writing exposure device, without In the case where the adjustment of composition, the excellent corrosion-resisting pattern of resist shape (resolution ratio) is formd with identical light exposure.In addition, Adaptation, the insulating properties for being formed by corrosion-resisting pattern are excellent, and then in soldering heat resistance, resistance to cracking, solvent resistance, acid resistance It and is the evaluation of " 3 " in the evaluation of alkali resistance, it is known that be excellent.In this way, the photosensitive polymer combination of present embodiment It especially can be preferably used as the production of permanent mask resist, and no matter use projection exposure device and direct-writing exposure dress Any one set, the fine tuning without composition can play excellent characteristic.In contrast, without benzophenone cpd The photosensitive polymer combination of the Comparative Examples 1 to 5 is when using projection exposure device, although in resist shape (resolution ratio) It is including resist shape when showing the performance same with embodiment, but using direct-writing exposure device with identical light exposure Effect inequality in the complete characteristic of (resolution ratio).
(embodiment 9~18, comparative example 6~10)
Using methyl ethyl ketone to match the Examples 1 to 9 of preparation, each photoresist of the Comparative Examples 1 to 5 shown in table 1 Composition is diluted, and is coated on polyethylene terephthalate (PET) film with a thickness of 25 μm, dry 10 at 90 DEG C Minute, form the photosensitive layer formed by photosensitive polymer combination with a thickness of 25 μm.In turn, film (15 μ are fitted on it The polypropylene screen of m), the dry film of embodiment 9~18, comparative example 6~10 is made respectively.
[dry film evaluation]
Cover film is removed from the above-mentioned dry film obtained, by the dry film heat lamination (75 DEG C, 0.4MPa) in whole face Copper clad laminate on, then, be carried out similarly exposure with the method recorded in above-mentioned [production of test film], production has permanently The test film of mask resist.
Using resulting test film, evaluation similarly to Example 1 is carried out.It shows the result in table 3.
Table 3
As shown in table 3, this implementation of the embodiment 10~18 of benzophenone cpd has been used as photopolymerization sensitizer No matter the dry film of mode uses any one of projection exposure device and direct-writing exposure device, in the tune without composition In the case where whole, the excellent corrosion-resisting pattern of resist shape (resolution ratio) is formd with identical light exposure, moreover, being formed by Adaptation, the insulating properties of corrosion-resisting pattern are excellent, and then in soldering heat resistance, resistance to cracking, solvent resistance, acid resistance and alkali resistance Evaluation in be " 3 " evaluation, it is known that be excellent.In this way, the dry film of present embodiment especially can be preferably used as forever The production of long mask resist, and no matter use any one of projection exposure device and direct-writing exposure device, equal nothing The fine tuning that need to be formed can play excellent characteristic.In contrast, the dry type of the comparative example 6~10 without benzophenone cpd Film is when using projection exposure device, although showing the performance same with embodiment in resist shape (resolution ratio), But when using direct-writing exposure device with identical light exposure, effect is equal in the complete characteristic for including resist shape (resolution ratio) Difference.

Claims (19)

1. a kind of photosensitive polymer combination, contain (A) epoxy resin containing sour modified vinyl, (B) Photoepolymerizationinitiater initiater, (C) the photopolymerization sensitizer containing benzophenone cpd and (D) photopolymerizable compound.
2. photosensitive polymer combination according to claim 1, wherein benzophenone chemical combination contained by (C) ingredient Object is to be selected from amino, ethylamino, dimethylamino, diethylamino, dibutylamino, hydroxyl, methoxy at least one The benzophenone cpd of group in base, ethyoxyl, butoxy and phenyl.
3. photosensitive polymer combination according to claim 1 or 2, wherein (A) ingredient, which contains to be selected from, uses bis-phenol At least one kind of epoxy resin (A1) and use containing sour modified vinyl of phenolic resin varnish type epoxy resin (a1) synthesis is different from In at least one kind of epoxy resin (A2) containing sour modified vinyl of epoxy resin (a2) synthesis of the epoxy resin (a1) extremely It is a kind few.
4. photosensitive polymer combination according to claim 3, wherein the epoxy resin (a2) is selected from novolaks It is at least one kind of in type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin and tris-phenol type epoxy resin.
5. photosensitive polymer combination according to claim 3 or 4, wherein the asphalt mixtures modified by epoxy resin containing sour modified vinyl Rouge (A1) be make containing saturation or unsaturated group multi-anhydride (c) and make the epoxy resin (a1) and containing the unitary of vinyl Resin (A1 ') made of carboxylic acid (b) reaction reacts and the resin that is formed, the epoxy resin containing sour modified vinyl (A2) be make containing saturation or unsaturated group multi-anhydride (c) with make each epoxy resin (a2) and containing vinyl one Resin (A2 ') made of the reaction of first carboxylic acid (b) reacts and the resin that is formed.
6. the photosensitive polymer combination according to any one of claim 3~5, wherein the bis-phenol phenolic varnish type Epoxy resin (a1) is selected from the bis-phenol phenolic resin varnish type epoxy resin with structural unit shown in the following general formula (I) and to have It is at least one kind of in the bis-phenol phenolic resin varnish type epoxy resin of structural unit shown in the following general formula (II),
In logical formula (I), R11Indicate hydrogen atom or methyl, Y1And Y2Hydrogen atom or glycidyl are each independently represented, it is multiple R11It may be the same or different, Y1And Y2At least one of indicate glycidyl,
In logical formula (II), R12Indicate hydrogen atom or methyl, Y3And Y4Hydrogen atom or glycidyl are each independently represented, it is multiple R12It may be the same or different, Y3And Y4At least one of indicate glycidyl,
The epoxy resin (a2) is selected from the nobolak type epoxy tree with structural unit shown in the following general formula (III) Rouge, the bisphenol-type epoxy resin with structural unit shown in the following general formula (IV) and have the following general formula (V) shown in structure It is at least one kind of in the tris-phenol type epoxy resin of unit,
In logical formula (III), R13Indicate hydrogen atom or methyl, Y5Indicate hydrogen atom or glycidyl, and hydrogen atom and shrink are sweet The molar ratio of oil base is calculated as 0/100~30/70 with hydrogen atom/glycidyl,
In logical formula (IV), R14Indicate hydrogen atom or methyl, Y6Indicate hydrogen atom or glycidyl, and hydrogen atom and glycidol The molar ratio of base is calculated as 0/100~30/70 with hydrogen atom/glycidyl, multiple R14It may be the same or different,
In logical formula (V), Y7Indicate hydrogen atom or glycidyl, multiple Y7It may be the same or different, at least one Y7It is sweet to shrink Oil base.
7. the photosensitive polymer combination according to any one of claim 3~6, wherein (A) ingredient contains at least Epoxy resin (A1) and at least one kind of epoxy resin (A2) containing sour modified vinyl containing sour modified vinyl described in a kind.
8. photosensitive polymer combination according to claim 7, wherein the bis-phenol phenolic resin varnish type epoxy resin (a1) With structural unit shown in the logical formula (I), and the epoxy resin (a2) is to contain structure shown in the logical formula (IV) The bisphenol A type epoxy resin or bisphenol f type epoxy resin of unit.
9. the photosensitive polymer combination according to any one of claim 3~6, wherein (A) ingredient contains at least Epoxy resin (A2) containing sour modified vinyl described in a kind.
10. photosensitive polymer combination according to claim 9, wherein the epoxy resin (a2) is with described logical The phenolic resin varnish type epoxy resin of structural unit shown in formula (III).
11. photosensitive polymer combination described according to claim 1~any one of 10, wherein (B) photopolymerization causes Agent be selected from alkyl phenones system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater, luxuriant titanium system's Photoepolymerizationinitiater initiater and It is at least one kind of in oxime ester system Photoepolymerizationinitiater initiater.
12. photosensitive polymer combination described according to claim 1~any one of 11, wherein (B) photopolymerization causes Agent is in alkyl phenones system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and oxime ester system Photoepolymerizationinitiater initiater It is at least one kind of.
13. photosensitive polymer combination described according to claim 1~any one of 12, wherein (B) photopolymerization causes Agent is acylphosphine oxide system Photoepolymerizationinitiater initiater.
14. photosensitive polymer combination described according to claim 1~any one of 13 further contains (E) pigment.
15. photosensitive polymer combination described according to claim 1~any one of 14, further contain that (F) is inorganic to be filled out Fill object.
A kind of photoresist group 16. dry film, with carrier film and described in any one of having used claim 1~15 Close the photosensitive layer of object.
17. a kind of printed wiring board has the photosensitive polymer combination as described in any one of claim 1~15 and is formed Permanent mask resist.
18. printed wiring board according to claim 17, wherein the permanent mask resist with a thickness of 10 μm with On.
19. a kind of manufacturing method of printed wiring board, successively has following processes:
Using described in photosensitive polymer combination or claim 16 described in any one of claim 1~15 on substrate Dry film is arranged the process of photosensitive layer；
The process for forming corrosion-resisting pattern using the photosensitive layer；And
The process for being solidified to form permanent mask resist is carried out to the corrosion-resisting pattern.
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